Anthraquinonyl triazine dyes

ABSTRACT

The invention relates to compounds of the formula

United States Patent Ulrich 54] ANTHRAQUINONYL TRIAZINE DYES [72] Inventor: Paul Ulrich, Magnolienpark l0, Basel, Switzerland [22] Filed: Jan. 27, 1970 [21] Appl. No.: 6,288

[30] Foreign Application Priority Data Jan. 31, 1969 Switzerland ..l563/69 [52] US. Cl......260/249, 260/256.4 R, 260/256.4 Q,

260/262, 260/153, 8/34 [51] Int. Cl. ..C07d 55/20 [58] Field of Search ..260/249 [56] References Cited UNITED STATES PATENTS 3,384,638 5/1968 Mix ..260/249 51 Aug. 15,1972

Primary Examiner.lohn M. Ford Attorney-Harry Goldsmith, Joseph G. Kolodny and Mario A. Monaco [57] ABSTRACT The invention relates to compounds of the formula A --B--RB---A 9 Claims, No Drawings ANTHRAQUINONYL TRIAZINE DYES The present application provides new compounds of the general formula (l)- -A,--B R B A wherein A, and A, each denotes a residue of a polycyclic quinone, of which at least one must be vattable, B denotes a fivemembered or six-membered heterocyclic ring which contains at least one ring nitrogen atom, and R denotes the residue of a polyfunctional hydroxyl or mercapto compound which is bound through two of its oxygen or sulphur atoms to a carbon atom of the residue B.

groups or halogen atoms, with polyfunctional hydroxyl or mercapto compounds and polycyclic quinones which contain condensable groups.

Suitable heterocyclic compounds having a five-membered or six-membered ring which contains at least 1 benzene ornaphthalene series or a" five-membered or six-membered heterocyclic residue having 1 to 3 hetero-atoms.

The heterocyclic residues B can contain further substituents for example alkyl or aryl groups, amino groups, for example alkylamino groups, arylarnino groups or a free HgN' group, alkoxy groups, and etherified hydroxyl or mercapto groups, for example alkylmercapto groups or arylmercapto groups. In particular, B may also contain a second residue of a polycyclic quinone which is identicalto that bound to B according to Formula l Preferably, B is the residue of a heterocyclic compound of the general formula f N. bl I wherein X, denotes the group in'which R denotes a hydrogen atom or a substituent for example a halogen atom, or a nitro, cyano, COClor alkyl group, for example a methyl group, or of the general formula V wherein the residues of formulas (2) and (3) can conand preferably 2 or 3 ring nitrogen atoms, and which contains at least two easily removable substituents, are above all compounds of the general. formulas and wherein X, has the above mentioned significance, and Y Y and Y each denotes a hydrogen atom ora substituent, for example a low molecular alkyl group, a

phenyl, naphthyl, phenylazo, alkoxy, aryloxy,

- arylamino or arylmercapto group, but wherein two of the substituents Y Y and Y each denotes an easilyremovable substituent (for example a methanesulphonyl, benzenesulphonyl or $0 11 group, an etherified mercapto group, or an R,CS S- group (R amino or alkyl), and also a sulphinic acid grouping or an ammonium or hydrazinium grouping, but above all a halogen atom, for example a chlorine or bromine atom The heterocyclic rings of formulas (4) and (5) can also contain a fused carbocyclic ring as indicated by the broken line.

As heterocyclic compounds which are suitable for the present process there may be mentioned: halogen derivatives of thiazoles, especially benzthiazole, oxazoles, imidazolesand benzimidazoles, chloro-red acid chloride, 2,4-dichloro pyrimidine, 3 ,6- dichloropyridazine, 3,6-dichloropyridazine-5-carboxylic acid chloride, tetrachloropyridazine, 4,5-dichloropyrida zon-(6)-yl-propionic acid chloride, 4,5- dichloro-l-phenylpyridazone-carboxylic acid chloride or -sulphonic acid chloride, 4,5-dichloropyridazonepropionic acid chloride, l,4-dichlorophthalazine-carboxylic acid chloride or -sulphonic acid chloride, 2,3- dichloroquinoxaline-carboxylic acid chloride or sulphonic acid chloride, 2,4-dichloroquinazoline-carboxylic acid chloride or sulphonic acid chloride, 2,4,6- trichloropyrimidine or 2,4,6-tribromopyrimidine and their derivatives which for example carry a cyano, nitro, methyl, ethyl, carbarnide, sulpharnide, carbomethoxy, carbalkoxy, acyl (for example benzoyl, acetyl or propionyl), alkenyl (for example allyl or chlorovinyl) or a substituted alkyl (for example carboxyrnethyl, chloromethyl or bromomethyl) group in the 5-position, 2,4,5,6-tetrachloropyrimidine or 2,4,5,6- tetrabromopyrimidine, 2,6-dichloroor 2,6-dibromo-4- carboethoxypyrimidine, 2,4,5-trichloropyrimidine, 5- nitro-6-rnethyl-2,4-dichloropyrimidine, 2,4- dichloropyrimidine-6-carboxylic acid chloride, 2,4- dichloropyrimidine-S-carboxylic acid chloride, 2,6- dichloropyrimidineor 2,6-dibromopyrimidine-4- or S-carboxylic acid amides or -sulphonic acid amides or 4- or -5-carboxylic acid chloride or -sulphonic acid chloride, 2,4-dichloropyrimidine-S-sulphonic acid, 2,4-

dichloro-5-chloromethyl-6 -methylpyrimidine, 2,4- dibromo-S-bromomethyl-6-methylpyrimidine, 2,4- dichloro-S-chloromethylpyrimidine, 2,4-dibromo-5- bromomethylpyrimidine, 2,5,6-trichloro-4-methylpyrimidine, 2,6-dichloro-4-trichloromethylpyrimidine or especially 2-methanesulphonyl-4,5-dichloro-6- methylpyrimidine, 2,4-dimethanesulphonyl-S-chloro-6 -methylpyrimidine, 2,4,6-trichlorol ,3 ,S-tria zine or 2,4,6-tribromo-l ,3 ,S-triazine, 4,6-dichlorol ,3,5- triazines which are substituted in the 2- position by an aryl or alkyl residue, for example a phenyl, methyl or ethyl residue, or by the residue of an aliphatic or aromatic mercapto compound bound through the sulphur atom or hydroxyl compound bound through the oxygen atom, or especially by a -NH group or by the residue of an aliphatic, hetero-aliphatic or aromatic amino compound bound through the nitrogen atom. As such compounds, the residues of which can be bound to the triazine nucleus in the 2-position by reaction with trihalogenotriazines, the following may for example be mentioned: aliphatic or aromatic mercapto or hydroxyl compounds, for example thioalcohols, thioglycollic acid, thiourea, thiophenols, methyl alcohol, ethyl alcohol, isopropyl alcohol, glycollic acid, phenol, chlorophenols or nitrophenols, phenol carboxylic acids and phenol sulphonic acids, naphthols, naphthol sulphonic acids and the like, but especially ammonia and compounds containing an amino group which can be acylated, for example hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulphonic acids, carbamic acid and its derivatives, semiand thiosemicarbazides and -carbazones, methylamine, ethylamine, isopropylamine, methoxyethylamine, methoxypropylamine, dimethylamine, diethylamine, methylphenylamine, ethylphenylamine, chloroethylamine, ethanolamine, propanolamine, benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminocarbonic acid esters, aminoacetic acid ethyl ester, aminoethane sulphonic acid, N-methylaminoethane sulphonic acid, but above all aromatic amines, for example aniline, N methylaniline, toluidines, xylidenes, chlororanilines, pand m-aminoacetanilide, nitroanilines, aminophenols, nitrotoluidines, phenylenediamines, toluylenediamines, anisidine, phenetidine, diphenylamine, naphthylamines, aminonaphthols and diaminonaphthalenes. Further, also colored compounds having dyestuff characteristics, for example 4- nitro-4'-aminostilbene disulphonic acid and aminoazo dyestuffs or aminoanthraquinones or phthalocyanines which still contain at least one reactive amino group.

Suitable polyfunctional hydroxyl or mercapto compounds which can be used for the manufacture of the compounds according to the invention are above all carbocyclic or heterocyclic compounds which contain at least two condensable OH groups, cyclic compounds having a glucoside link, but especially aromatic or heterocyclic compounds which contain at least two hydroxyl groups having replaceable hydrogen atoms.

The following compounds may be mentioned: dihydroxybenzenes and trihydroxybenzenes, for example resorcinol, hydroquinone and their substitution products, phloroglucinol, pyrogallol and substitution Dihydroxydiplienylpropane lhnnolphthalein Fluoroscnln l Ellagic acid or dihydroxyazo or polyazo dyestuffs, for example and their substitution products, 1,3-, 1,4- and 1,5- dihydroxynaphthalene, 2,6-dihydroxytoluene, dior tri-hydroxyor mercapto-heterocyclics, for example 2- phenyl-4,6-dihydroxytriazine, 2,4,6-tn'hydroxypyrimidine, 2,4,6-trihydroxytriazine, 3,6-dihydroxypyridazine, 1,4-dihydroxyphthalazine, 1,3-dihydroxyquinazoline, 2,3-dihydroxyquinoxa1ine, 2,5-dimercaptol ,3 ,4-thiadiazole, 3 ,6-dihydroxyl ,2,4-trimethylbenzene, 4-methyluracil, di-B-naphthol, tetrahydroxybiphenyl and trihydroxybenzoic acid.

Instead of a dihydroxy or dimercapto compound, compounds which contain both a hydroxyl group and a mercapto group may also be used, for example, 2-mercapto-4-hydroxypyrimidine, 2-thiouracil or 4- methylthiouracil, so that compounds of Fonnula (l) are produced wherein R is on the one hand bound through an oxygen atom and on the other hand through a sulphur atom to the particular residue B.

Among the polycyclic quinones, those which are vattable are of particular importance. To manufacture the dyestuffs according to the invention, quinones containing condensable substituents, for example primary or secondary amino groups, may be reacted with the above mentioned compounds which contain easily removable substituents, for example halogen atoms, in known manner. The vattable quinones include those which contain chromophores which by reduction can be converted into a so-called leuco-form or vat, which possesses a better affinity for natural or regenerated cellulose fibers than the non-reduced form, and which can be converted back into the original chromophoric system by oxidation. Thus no polycyclic quinones of the type of lamino-4-arylaminoanthraquinone2- sulphonic acid are used in the present process, because, whilst these can be reduced, they are chemically so greatly modified by the reduction that they can no longer be converted back into the original chromophoric system. As examples of vattable polycyclic quinones, the following may be mentioned: perylenetetracarboxylic acid imides, above all the phenylimides, anthrapyrimidines, anthrapyridones, isothiazolanthrones, quinazolinanthraquinones, x-

azolanthraquinones, thiazolanthraquinones, oxdiazolanthraquinones, anthraquinonyl-triazoles, pyrazolanthraquinones, dipyrazolanthronyls, pyrazinoanthraquinones, azabenzanthrones, in-

danthrones, thioxanthonanthraquinones, anthrimides, anthrimidecarbazoles, dihydroacridines, anthanthrones, pyranthrones, dibenzpyrene-quinones, dibenzanthrones, isodibenzanthrones, flavanthrones, acedianthrones and especially anthraquinoneacridones and the anthraquinones themselves, whereby there are to be understood not only derivatives having pure 9,10- dioxoanthracene rings but also those with thiophanthrone residues and the like, as well as anthraquinone compounds which contain 9,10-dioxoanthracene rings which can carry the usual substituents, for example halogen atoms, alkoxy groups, alkyl groups, sulphonic acid amide groups, sulphone groups and acylamino groups as well as further fused and condensedon carbocyclic and heterocyclic rings. As examples of suitable quinones which possess condensable amino groups, there may be mentioned: 1- amino-Z-chloroanthraquinone, l-amino-3- chloroanthraquinone, 2-amino-3-chloroanthraquinone, l-amino--chloroanthraquinone, 2-amino-4- chloroanthraquinone, l-amino-4-chloroanthraquinone, 1-amino-6-chloroanthraquinone, l-arnino-8l chloroanthraquinone, l-amino3 -chloro-6- methylanthraquinone, l-amino-6,7- dichloroanthraquinone, l-amino-4- benzoylaminoanthraquinone, l-amino-4-methoxyanthraquinone, 2-amino-3,4-phthaloylacridone, l,4- diamino-2-acetylaminoanthraquinone,

aminoanthrapyrimidine, l-aroylamino-4- or -5- aminoanthraquinones, l ,4-diamino-2- acetylanthraquinone, l-aminoJ-chloroanthraquinone,

6 l-amino-2-methyl-3-chloroanthraquinone, 4- aminoanthraquinone-2,l(N)-acridones, 4,4'-, 4,5'- or 5,5'-diamino-l l '-dianthrimidecarbazole, aminopyranthrones, mono-and diaminoacedianthrone, aminoisodibenzanthrone, aminodibenzanthrone, aminoanthanthrone, aminoflavanthrone, aminopyranthrone, 4-, 5- or 8-amino-l,l '-dianthrimide-carbazole, 4- or 5-amino5'-benzoylamino-dianthrimidecarbazole, 4-amino-4'-benzoylamino-dia.nthrimide-carbazole, aminodibenzpyrene-quinone, and also monoand diaminotrianthrimidecarbazoles, for example 8,8 "-diamino-l ',1,4,l"-trianthrimidecarbazole, and also perylenetetracarboxylic acid di-(por m-aminophenyl)-amide, the compounds of the formulas N112 N ll l X I x=o or s) NIH and I -NII2 wherein one of the symbolsR represents a hydrogen atom and the other represents a grouping of the formula n=1 or 2 one of the symbols R R and R represents a halogen atom, an alkoxy, aryloxy, arylmercapto or acylamino group, especially a benzoylamino group, for example a chloro-, methyl-, sulpho-or fluoro-benzoylamino group or the unsubstituted C H -COgroup itself, and the other symbol R R or R represents a hydrogen or halogen atom, one of the pairs of symbols R R R R or R R together being able to represent a grouping and R denotes an arylene residue, preferably of the benzene series, the compound wherein R can be a benzoyl group or a hydrogen atom, aminoisothiazolanthrones and amino-indanthrones.

The condensation reactions may be advantageously carried out in an inert solvent and in the presence of an acid-binding agent, for example sodium carbonate, sodium acetate, or advantageously a tertiary amine, preferably pyridine.

The reaction of the heterocyclic compounds of formulas (4) and (5) or of the derivatives of the acids mentioned with the hydroxy or mercapto compounds and the polycyclic quinones can take place in any desired sequence. Advantageously, however, the reaction with the hydroxy or mercapto compounds corresponding to the residue R takes place last. Thus for example, 2 mols of a monohalogen compound of the formula may be condensed by heating with 1 mol of a dihydroxy compound in an organic medium, for example chlorobenzene, nitrobenzene, N-methylpyrrolidone, pyridine, quinoline and the like.

It can be of advantage to pass a stream of air or nitrogen through the reaction mixture periodically or for the entire duration of the reaction. Under certain circumstances it can also be advantageous to add acidbinding substances to the reaction mixture, for example alkalis (sodium carbonate, potassium carbonate and others) or such compounds which facilitate the acid splitting, for example tertiary bases (pyridine and others) or dimethylformamide and the like.

The compounds according to the invention are excellent vat dyestuffs and pigment dyestuffs. The dyestuffs can also contain sulphonic acid groups. Occasionally, products having better fiber affinity are obtained when compounds free from sulphonic acid groups are subsequently sulphonated according to one of the usual processes. The dyeings obtained with the compounds according to the invention are distinguished by vivid clear shades. Their advantageous application properties should be particularly emphasized. The present process yields inter alia dyestuffs which can be applied independently of the temperature. They can be applied according to the most diverse processes, for example the exhaustion process or according to the pad dyeing process, for example the pad-jig process, the pad-steam process or the cold dwell process. It is equally noteworthy that good dyestufi yields are achieved in all application processes. It is also noteworthy that a high proportion of the compounds can be synthesized in almost theoretical yield according to the invention. It is a particular advantage that the range of color shades is very great, so that using the compounds according to the invention practically all color shades can be produced. Dyestuffs can. also be obtained inter alia which in comparison with the hydroxy compounds which have only been reacted on one side with a heterocyclic component possess more level dyeing properties, and also dyestuffs which reserve very well on polyester material.

The products obtained according to the process are suitable for dyeing and printing the most diverse materials, in particular for dyeing and printing fibers of 5 natural and regenerated cellulose in the presence of reducing agents, for example dithionite. The dyeings obtained are distinguished by very good properties of wet fastness, especially fastness to boiling with soda and fastness to chlorine, and also by good to very good light fastness properties, and in many cases by a remarkably good behavior on industrial laundering."

The new compounds can also be used as pigments. As a result of their advantageous properties they can be used for the most diverse pigment applications, for example in a finely divided fomi for the dyeing of acetate rayon and viscose or cellulose ethers or cellulose esters or polyamides or polyurethanes or polyesters in the spinning composition, and also for the manufacture of colored lacquers or lacquer-forming agents, solutions or products of acetylcellulose, nitrocellulose, natural resins or synthetic resins, for example polymerization resins or condensation resins, for example aminoplasts, alkyd resins, phenoplasts, polyolefines, for example polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyacrylonitrile, rubber, casein, silicone and silicone resins. They can furthermore advantageously be used in the manufacture of crayons, cosmetic preparations or laminated sheets. The compounds according to the invention also include, amongst others, pigment dyestuffs which are distinguished by their excellent migration behavior in fabrics coated with polyvinyl chloride.

In the Examples which follow the parts always denote parts by weight.

EXAMPLE 1 l 1.2 Parts of the reaction product of 1 mol of cyanuryl chloride and 2 mols of l-aminoanthraquinone are 40 heated to the boil in 100 parts of nitrobenzene together with 1.1 parts of hydroquinone with the addition of 0.3 part of pyridine, whilst passing a gentle stream of nitrogen through the mixture. The mixture is kept at the reaction temperature for 5% hours whilst stirring, 45 allowed to cool to about 100 C. and filtered hot, the product is washed with nitrobenzene and subsequently with methanol and dried in vacuo.

A yellow dyestuff of the constitution is obtained, which is taken up by cellulose-containing textiles using the customary vat dyeing processes to give clear yellow shades.

9 l0 EXAMPLE 2 The reaction charge is worked-up in accordance with Example 1. 6.3 Parts of the reaction product of l mol of cyanuryl Th isolated dyestulf of the constitution I II O bill-I, 11111 0 /C=N on, N- t' o-N (1H3 =o i i i i chloride and2mols of l-amino-3-chloroanthraquinone dyes cotton and regenerated cellulose fibers in acare heated to the boil in 80 parts of nitrobenzene cordance with the vat dyeing processes clear greenishtogether with 1.2 parts of 4,4'-dihydroxydiphenyltinged yellow shades.

propane with the addition of 0.3 part of pyridine. The 25 Using the starting substances mentioned in the Table mixture is stirred for 2 hours at the reaction temperawhich follows, further dyestuffs can be manufactured ture while periodically passing a gentle stream of in the manner according to the invention, their color nitrogen through the reaction vessel. shades being given in the last column.

Colour Reactive Component Dihydroxy Compound Shade 1. Ito-Q0903 yellow Colour Reactive Component DihydroxyCompound Shade ll 0 NH red I C- v 0-0]. ((z: N 0 NH ll 6 blue yellow j I Di--, Trior Polyhydroxy or 2 3232 Reative Component 5 -mercapto Compound green HO OH Reactive component Di-, Trior Polyhydroxy or $2113? -mercapto Compound.

0 23 HO OH [I (lg/U yellow 1 0 NH u I C- N O N C-Cl ll f N O NH ll ll 0 24 in HO OH yellow COOH 25 1! HQ ()H/O yellow OH OH 26. m yellow Reactive Component D -w Tri- OI I Polyhydroxy or gfiigg -mercapto Compound 0 OH OH 2 II II C1 Cl 0 I|\IH Cl C].

0- N N C-Cl I N O NH II 28 HO OH yellow 9 yellow Reactive Component Di-, Trior Polyhydroxy or gigg -mercapto Compound 3 c1 0 01 30 HO OH yellow ll 0 NH O I C- N 0 N C-Cl f N O NH II CH CH 31 HO 3 1m yellow 32 yellow Reactive Component 7 Di- Trio Colour Polyhydroxy or i -mer.capto Compound: i Shade f. H0 0 33 ll yellow ll HO o1 OH 0 IiTH I 3 Mols N I N 0 NH 34 3 Idols H yellow 35 3 Mols II w yellow C N N 8 C OH N HQ Reactive Component Di-, Trior Polyhydroxy or $3 32 '-mercapto Compound 40 r H greenishtinged o H yellow H N-(\) ll C. N O 1 ll 01 41 r greenlsh- NC CN tinged n HOGOH y 0 rlm C- N N C-Cl f N O NH ll H C].

42 HOWE greenishtinged yifllnw greenishtinged Nan :3 I. H yellow 

2. A compound according to claim 1 of the formula
 3. A dyestuff as claimed in claim 1 of the formula
 4. A dyestuff as claimed in claim 1 of the formula
 5. A compound of the formula:
 6. A compound as claimed in claim 5, wherein X denotes a chlorine atom bound in the 3-position.
 7. A dyestuff as claimed in claim 5 of the formula
 8. A dyestuff as claimed in claim 5 of the formula
 9. A dyestuff as claimed in claim 5 of the formula 